US4292232A - Process for the mass coloration of thermoplastics with anthraquinonylaminotraizines - Google Patents

Process for the mass coloration of thermoplastics with anthraquinonylaminotraizines Download PDF

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US4292232A
US4292232A US06/093,644 US9364479A US4292232A US 4292232 A US4292232 A US 4292232A US 9364479 A US9364479 A US 9364479A US 4292232 A US4292232 A US 4292232A
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anilino
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Joachim Dazzi
Max Jost
Arnold Wick
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BASF Corp
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Ciba Geigy Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16Amino-anthraquinones
    • C09B1/20Preparation from starting materials already containing the anthracene nucleus
    • C09B1/36Dyes with acylated amino groups
    • C09B1/46Dyes with acylated amino groups the acyl groups being residues of cyanuric acid or an analogous heterocyclic compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/51N-substituted amino-hydroxy anthraquinone
    • C09B1/516N-acylated derivatives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/54Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
    • C09B1/547Anthraquinones with aromatic ether groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/56Mercapto-anthraquinones
    • C09B1/58Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals
    • C09B1/585Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals substituted by aryl radicals

Definitions

  • Suitable linear polyesters are in particular those which are obtained by polycondensation of terephthalic acid or an ester thereof with a glycol of the formula HO--(CH 2 ) n --OH, in which n is an integer from 2 to 10, or with 1,4-di(hydroxymethyl)cyclohexane, or by polycondensation of a glycol ether of a hydroxybenzoic acid, for example p-( ⁇ -hydroxyethoxy)-benzoic acid.
  • the term "linear polyesters” also comprises copolyesters which are obtained by partial replacement of terephthalic acid by another dicarboxylic acid or by a hydroxycarboxylic acid and/or by partial replacement of the glycol by another diol.
  • the preferred linear polyester are polyethylene terephthalates.
  • the colouration obtained, especially in polyester, are distinguished by good fastness to light, washing, dry cleaning, cross-dyeing, thermofixation, bleeding and chlorite bleaching, as well as by clear shades and good colour strength.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coloring (AREA)

Abstract

A process for the mass coloration of thermoplastics with anthraquinonylaminotriazines of the formula ##STR1## wherein each of X1 and X2 is an alkylmercapto or arylmercapto group or a group of the formula --NR1 R2, in which each of R1 and R2 is alkyl, cycloalkyl, aralkyl or aryl, and R2 can additionally be hydrogen, or R1 and R2 together with the nitrogen atom to which they are attached and optionally a further heteroatom form a 5- or 6-membered ring, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR2## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1. Yellow to orange colored fibres of clear shade, good color strength and fastness properties are obtained.

Description

The present invention relates to a process for the mass colouration of thermoplastics with anthraquinonylaminotriazines of the formula ##STR3## wherein each of X1 and X2 is an alkylmercapto or arylmercapto group or a group of the formula --NR1 R2, in which each of R1 and R2 is alkyl, cycloalkyl, aralkyl or aryl, and R2 can additionally be hydrogen, or R1 and R2 together with the nitrogen atom to which they are attached and optionally a further heteroatom form a 5- or 6-membered ring, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR4## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1.
Alkylmercapto groups represented by X1 and X2 in formula (1) are preferably those containing 1 to 6 carbon atoms. Suitable arylmercapto groups are e.g. naphthylmercapto groups and, in particular, phenylmercapto groups which are unsubstituted or substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms. Where X1 and X2 are groups of the formula --NR1 R2, the preferred meanings of R1 and R2 are alkyl groups of 1 to 20 carbon atoms, alkoxyalkyl groups, cycloalkyl groups of 5 to 10 carbon atoms, benzyl or phenylethyl groups, or phenyl groups which are unsubstituted or substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms, while R2 can additionally be hydrogen.
The two radicals R1 and R2 together with the nitrogen atom to which they are attached can also form e.g. a piperidine or morpholine ring.
An arylmercapto group Y is preferably a phenylmercapto group which can be substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms. Y can also be an alkanoylamino group of 2 to 6 carbon atoms or a benzoylamino group which is unsubstituted or substituted by chlorine atoms or alkyl or alkoxy atoms of 1 to 6 carbon atoms, but is in particular a hydrogen atom or a OH group. n is preferably 0.
The anthraquinonylaminotriazine compounds to be used in accordance with the invention are known compounds. They are advantageously obtained by condensation of a chlorotriazine of the formula ##STR5## with the corresponding aminoanthraquinone, for example 1-aminoanthraquinone, 1-aminoanthraquinone-3-, -4-, -5-, -6- or -7-chloroanthraquinone, 1-aminoanthraquinone-4-hydroxyanthraquinone, 1-aminoanthraquinone-4-, -5- or -8-phenylmercaptoanthraquinone, 1-aminoanthraquinone-4- or -5-acetylaminoanthraquinone, 1-aminoanthraquinone-4- or -5-benzoylaminoanthraquinone.
The triazines of the formula (2) are obtained by the stepwise replacement of two chlorine atoms in cyanuric chloride by the amines or mercaptans X1 H and X2 H.
The following amines are cited as examples: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-hexadecylamine, or n-octadecylamine, dimethylamine, diethylamine, di-n-propylamine or di-n-butylamine, β-methoxyethylamine, γ-methoxy-n-propylamine or γ-isopropoxy-n-propylamine, cyclohexylamine, dicyclohexylamine, benzylamine, phenylethylamine, aniline, o-, m- or p-toluidine, N-methylaniline, N-ethylaniline or N-n-butylaniline, 1-aminonaphthalene, piperidine or morpholine.
Table I lists a number of anthraquinonylaminotriazines of the formula ##STR6## wherein A is the 1-anthraquinonyl radical, m is 1, and the meanings of X1 and X2 are indicated in columns II and III.
              TABLE I                                                     
______________________________________                                    
No.    X.sub.1           X.sub.2                                          
______________________________________                                    
1    β-methoxyethylamino                                             
                       β-methoxyethylamino                           
2    γ-methoxypropylamino                                           
                       γ-methoxypropylamino                         
3    γ-isopropoxypropylamino                                        
                       γ-isopropoxypropylamino                      
4    benzylamino       benzylamino                                        
5    phenylethylamino  phenylethylamino                                   
6    n-hexadecylamino  n-hexadecylamino                                   
7    n-octadecylamino  n-octadecylamino                                   
8    methylamino       ethylamino                                         
9    methylamino       n-butylamino                                       
10   methylamino       n-hexadecylamino                                   
11   ethylamino        n-octadecylamino                                   
12   methylamino       dimethylamino                                      
13   methylamino       diethylamino                                       
14   methylamino       di-n-propylamino                                   
15   methylamino       di-n-butylamino                                    
16   ethylamino        dimethylamino                                      
17   methylamino       anilino                                            
18   ethylamino        anilino                                            
19   isopropylamino    anilino                                            
20   n-butylamino      anilino                                            
21   n-hexadecylamino  anilino                                            
22   n-octadecylamino  anilino                                            
23   methylamino       N-methyl-anilino                                   
24   ethylamino        N-methyl-anilino                                   
25   dimethylamino     diethylamino                                       
26   dimethylamino     diisopropylamino                                   
27   dimethylamino     di-n-butylamino                                    
28   dimethylamino     N-methyl-anilino                                   
29   di-isopropylamino N-methyl-anilino                                   
30   di-n-butylamino   N-methyl-anilino                                   
31   anilino           N-methyl-anilino                                   
32   N-methyl-anilino  N-ethyl-anilino                                    
34   ethylmercapto     methylmercapto                                     
35   ethylmercapto     n-propylmercapto                                   
36   ethylmercapto     n-butylmercapto                                    
37   ethylmercapto     n-hexadecylmercapto                                
38   ethylmercapto     n-octadecylmercapto                                
39   methylmercapto    phenylmercapto                                     
40   ethylmercapto     phenylmercapto                                     
41   anilino           phenylmercapto                                     
42   N-methylanilino   phenylmercapto                                     
43   N-ethylanilino    phenylmercapto                                     
44   methylamino       methylmercapto                                     
45   methylamino       ethylmercapto                                      
46   methylamino       n-propylmercapto                                   
47   methylamino       n-butylmercapto                                    
48   methylamino       n-hexadecylmercapto                                
49   methylamino       n-octadecylmercapto                                
50   ethylamino        methylmercapto                                     
51   diethylamino      methylmercapto                                     
52   dimethylamino     methylmercapto                                     
53   dimethylamino     ethylmercapto                                      
54   diethylamino      ethylmercapto                                      
55   di-n-butylamino   ethylmercapto                                      
56   dimethyamino      n-propylmercapto                                   
57   anilino           methylmercapto                                     
58   anilino           ethylmercapto                                      
59   anilino           n-propylmercapto                                   
60   anilino           n-butylmercapto                                    
61   anilino           n-hexadecylmercapto                                
62   anilino           n-octadecylmercapto                                
63   N-methylanilino   methylmercapto                                     
64   N-ethylanilino    methylmercapto                                     
______________________________________                                    
Table II lists further anthraquinonylaminotriazines of the formula (3), wherein m is 2, A is the anthraquinone radical which is bonded to the triazinylamino groups in the positions indicated in column II, and X1 and X2 have the meanings given in columns III and IV.
              TABLE II                                                    
______________________________________                                    
     Posi-                                                                
No.  tion     X.sub.1         X.sub.2                                     
______________________________________                                    
65   1,4    β-methoxyethylamino                                      
                            β-methoxyethylamino                      
66   1,5    β-methoxyethylamino                                      
                            β-methoxyethylamino                      
67   1,4    γ-methoxypropylamino                                    
                            γ-methoxypropylamino                    
68   1,5    γ-methoxypropylamino                                    
                            γ-methoxypropylamino                    
69   1,4    γ-isopropoxypropyl-                                     
                            γ-isopropxypropylamino                  
            amino                                                         
70   1,5    γ-isopropoxypropyl-                                     
                            γ-isopropxypropylamino                  
            amino                                                         
71   1,4    benzylamino     benzylamino                                   
72   1,5    benzylamino     benzylamino                                   
73   1,4    n-hexadecylamino                                              
                            n-hexadecylamino                              
74   1,5    n-hexadecylamino                                              
                            n-hexadecylamino                              
75   1,4    methylamino     methylamino                                   
76   1,5    methylamino     methylamino                                   
77   1,4    butylamino      butylamino                                    
78   1,5    butylamino      butylamino                                    
79   1,4    dimethylamino   dimethylamino                                 
80   1,5    dimethylamino   dimethylamino                                 
81   1,4    morpholyl       morpholyl                                     
82   1,5    morpholyl       morpholyl                                     
83   1,4    anilino         anilino                                       
84   1,5    anilino         anilino                                       
85   1,4    phenylmercapto  phenylmercapto                                
86   1,5    phenylmercapto  phenylmercapto                                
87   1,4    n-butylmercapto n-butylmercapto                               
88   1,5    n-butylmercapto n-butylmercapto                               
89   1,4    n-hexadecylmercapto                                           
                            n-hexadecylmercapto                           
90   1,5    n-hexadecylmercapto                                           
                            n-octadecylmercapto                           
91   1,4    n-octadecylmercapto                                           
                            n-octadecylmercapto                           
92   1,5    n-octadecylmercapto                                           
                            n-octadecylmercapto                           
93   1,4    methylamino     anilino                                       
94   1,5    methylamino     anilino                                       
95   1,4    methylamino     N-methylanilino                               
96   1,5    methylamino     N-methylanilino                               
97   1,4    dimethylamino   anilino                                       
98   1,5    dimethylamino   anilino                                       
99   1,4    methylmercapto  anilino                                       
100  1,5    methylmercapto  anilino                                       
101  1,4    methylmercapto  N-methylanilino                               
102  1,5    methylmercapto  N-methylanilino                               
103  1,4    n-butylmercapto anilino                                       
104  1,5    n-butylmercapto anilino                                       
105  1,4    n-octadecylmercapto                                           
                            anilino                                       
106  1,5    n-octadecylmercapto                                           
                            anilino                                       
107  1,4    methylmercapto  phenylmercapto                                
108  1,5    methylmercapto  phenylmercapto                                
109  1,4    n-butylmercapto phenylmercapto                                
110  1,5    n-butylmercapto phenylmercapto                                
111  1,4    methylmercapto  n-hexadecylmercapto                           
112  1,5    methylmercapto  n-hexadecylmercapto                           
113  1,4    methylamino     dimethylamino                                 
114  1,5    methylamino     dimethylamino                                 
115  1,4    methylmercapto  morpholinyl                                   
116  1,5    methylmercapto  morpholinyl                                   
117  1,4    n-hexadecylamino                                              
                            anilino                                       
118  1,5    n-hexadecylamino                                              
                            anilino                                       
119  1,4    isopropylamino  anilino                                       
120  1,5    isopropylamino  anilino                                       
121  1,4    anilino         N-methylanilino                               
122  1,5    anilino         N-methylanilino                               
123  1,4    methylamino     methylmercapto                                
124  1,5    methylamino     methylmercapto                                
125  1,4    dimethylamino   methylamino                                   
126  1,5    dimetylamino    methylamino                                   
127  1,4    dimethylamino   methylmercapto                                
128  1,5    dimethylamino   methylmercapto                                
129  1,5    ethylamino      butylamino                                    
______________________________________                                    
Table III lists compounds of the formula ##STR7## wherein X1 and X2 have the meanings given in columns II and III and Y is as defined in column IV. Column V indicates the position of Y.
              TABLE III                                                   
______________________________________                                    
No.   X.sub.1    X.sub.2    Y         Position                            
______________________________________                                    
130  ethylamino butylamino hydroxy    4                                   
131  cyclohexyl-                                                          
                cyclohexyl-                                               
                           hydroxy    4                                   
     amino      amino                                                     
132  dimethyl-  dimethyl-  2,4-bisanilino-                                
                                      4                                   
     amino      amino      triazinyl-6-                                   
                           amino                                          
133  N-methyl-  phenylamino                                               
                           2,4-bisethyl-                                  
                                      4                                   
     anilino               aminotriazinyl-                                
                           6-amino                                        
134  N-methyl-  phenylamino                                               
                           2,4-bisethyl-                                  
                                      5                                   
     anilino               aminotriazinyl-                                
                           6-amino                                        
135  N-methyl-  phenylamino                                               
                           2,4-bisphenyl-                                 
                                      4                                   
     anilino               mercapto-tria-                                 
                           zinyl-6-amino                                  
______________________________________                                    
It is also possible to use mixtures of different dyes.
Examples of thermoplastics are polyolefins, such as polyethylene, polypropylene or polyisobutylene, also polyvinyl chloride, polystyrene, as well as copolymers of styrene, such as ABS, and especially linear polyesters.
Suitable linear polyesters are in particular those which are obtained by polycondensation of terephthalic acid or an ester thereof with a glycol of the formula HO--(CH2)n --OH, in which n is an integer from 2 to 10, or with 1,4-di(hydroxymethyl)cyclohexane, or by polycondensation of a glycol ether of a hydroxybenzoic acid, for example p-(β-hydroxyethoxy)-benzoic acid. The term "linear polyesters" also comprises copolyesters which are obtained by partial replacement of terephthalic acid by another dicarboxylic acid or by a hydroxycarboxylic acid and/or by partial replacement of the glycol by another diol. However the preferred linear polyester are polyethylene terephthalates.
Colouration is effected by the conventional methods, for example by mixing the colourants with the plastics material in granulate or particulate form and extruding the mixture to fibres, sheets or granules. These latter can then be moulded to objects by injection moulding.
The colouration obtained, especially in polyester, are distinguished by good fastness to light, washing, dry cleaning, cross-dyeing, thermofixation, bleeding and chlorite bleaching, as well as by clear shades and good colour strength.
Russian Pat. No. 192.993 and German Auslegeschrift No. 1 644 532 describe anthraquinone dyes which in the 4-position contain an arylamino group. In contradistinction thereto, the colourants employed in the present invention colour polyester in shades of distinctly better fastness to light and resistance to atmospheric influences.
The invention is illustrated by the following Examples, in which parts and percentages are by weight.
EXAMPLE 1
A non-delustred polyethylene terephthalate granulate suitable for fibre manufacture is shaken in a closed vessel for 15 minutes on a mechanical shaker together with 1% of 1-(2',4'-bis-N-methyl-N-phenylamino-1',3',5'-triazinyl-6')-aminoanthraquinone. The uniformly coloured granules are then spun in a melt spinning machine (285° C.±3° C., sojourn time in the spinning machine about 5 minutes) to filaments, which are stretched and wound on a draw twister. The solubility of the colourant in polyethylene terephthalate results in a strong yellow colouration which is distinguished by outstanding light-fastness, excellent fastness to washing, dry cleaning, cross-dyeing, sublimation and rubbing after thermofixation, and also by excellent resistance to chlorite bleaching and good viscosity values.
EXAMPLE 2
1000 parts of polyethylene terephthalate granules, 10 parts of titanium oxide (Kronos RN 40) and 1 part of finely divided 1-(2',4'-bis-N-methyl-N-phenylamino-1',3',5'-triazinyl-6')-amino-4-hydroxyanthraquinone are mixed in a closed vessel for 2 hours on a roller gear table. The coloured granules are extruded at about 260° C. to strands of 2 mm, which are re-granulated. The resultant granules are processed at 270°-280° C. in a screw injection moulding machine to mouldings. The red coloration obtained is of very good light-fastness.
EXAMPLES 3-42
Table IV lists further colourants of the formula (3) which were used for colouring polyethylene terephthalate by the methods described in Examples 1 and 2. A is the anthraquinonyl radical. The meanings of X1, X2 and m are indicated in columns II, III and IV respectively. The position of the triazinylamino group in the anthraquinone radical is indicated in column V.
              TABLE IV                                                    
______________________________________                                    
Exam-                             Posi-                                   
ple    X.sub.1     X.sub.2    m   tion  Colour                            
______________________________________                                    
3     methylamino methylamino 1   1     yellow                            
4     methylamino methylamino 2   1,5   yellowish                         
                                        orange                            
5     ethylamino  ethylamino  1   1     yellow                            
6     ethylamino  ethylamino  2   1,5   yellowish                         
                                        orange                            
7     n-butylamino                                                        
                  n-butylamino                                            
                              1   1     yellow                            
8     dimethylamino                                                       
                  dimethylamino                                           
                              1   1     yellow                            
9     diethylamino                                                        
                  diethylamino                                            
                              1   1     yellow                            
10    diisopropyl-                                                        
                  diisopropyl-                                            
                              1   1     yellow                            
      amino       amino                                                   
11    di-n-butyl- di-n-butyl  1   1     yellow                            
      amino       amino                                                   
12    piperidyl   piperidyl   1   1     yellow                            
13    morpholyl   morpholyl   1   1     yellow                            
14    anilino     anilino     1   1     yellow                            
15    N-methylani-                                                        
                  N-methylani-                                            
                              1   1     yellow                            
      lino        lino                                                    
16    N-methylani-                                                        
                  N-methylani-                                            
                              2   1,4   violet                            
      lino        lino                                                    
17    N-methylani-                                                        
                  N-methylani-                                            
                              2   1,5   reddish                           
      lino        lino                  yellow                            
18    diphenylamino                                                       
                  diphenylamino                                           
                              1   1     yellow                            
19    phenylmercapto                                                      
                  phenylmercapto                                          
                              1   1     yellow                            
20    methoxypropio-                                                      
                  methoxypropio-                                          
                              1   1     yellow                            
      nylamino    nylamino                                                
21    isopropoxy- isopropoxy- 1   1     yellow                            
      propylamino propylamino                                             
22    methoxyethyl-                                                       
                  methoxyethyl-                                           
                              1   1     yellow                            
      amino       amino                                                   
23    amino       amino       1   1     yellow                            
24    benzylamino benzylamino     1     yellow                            
25    phenylethyl-                                                        
                  phenylethyl-                                            
                              1   1     yellow                            
      amino       amino                                                   
26    diisopropyl-                                                        
                  diisopropyl-                                            
                              2   1,5   orange                            
      amino       amino                                                   
27    diisopropyl-                                                        
                  phenylmercapto                                          
                              1   1     yellow                            
      amino                                                               
28    diisopropyl-                                                        
                  p-toluidino 1   1     yellow                            
      amino                                                               
29    dimethylamino                                                       
                  methylmer-  1   1     yellow                            
                  capto                                                   
30    methylmer-  methylmer-  1   1     yellow                            
      capto       capto                                                   
31    methylmer-  butyl-2-mer-                                            
                              1   1     yellow                            
      capto       capto                                                   
32    methylmer-  methylmer-  2   1,5   reddish                           
      capto       capto                 yellow                            
33    N-methyl-   N-methyl-   2   1,8   reddish                           
      anilino     anilino               yellow                            
34    methylmercapto                                                      
                  anilino     1   1     yellow                            
35    methylmercapto                                                      
                  phenylmercapto                                          
                              1   1     greenish                          
                                        yellow                            
36    methylmercapto                                                      
                  o-phenetidino                                           
                              1   1     greenish                          
                                        yellow                            
37    methylmercapto                                                      
                  p-phenetidino                                           
                              1   1     yellow                            
38    methylmercapto                                                      
                  4-chlorophenyl-                                         
                              1   1     yellow                            
                  mercapto                                                
39    methylmercapto                                                      
                  2,5-dichlor-                                            
                              1   1     yellow                            
                  phenyl                                                  
40    methylmercapto                                                      
                  4-methylphenyl                                          
                              1   1     yellow                            
41    phenylmercapto                                                      
                  morpholino  1   1     yellow                            
42    phenylmercapto                                                      
                  cyclohexyl-1-                                           
                              1   1     yellow                            
                  amino                                                   
______________________________________                                    
EXAMPLES 43-82
Table IV lists further colourants of the formula (4) which were used to colour polyethylene terephthalate by the methods described in Examples 1 and 2. A is the anthraquinonyl radical. The meanings of X1, X2 and Y are given in columns II, III and IV respectively. Column V indicates the position of Y in the anthraquinonyl radical and column VI the shade of the coloured polyester fibres.
              TABLE V                                                     
______________________________________                                    
Ex-                                 Po-                                   
am-                                 si-                                   
ple   X.sub.1    X.sub.2    Y       tion Colour                           
______________________________________                                    
43   ethylamino ethylamino hydroxy  4    red                              
44   ethylamino ethylamino benzoyl- 5    reddish                          
                           amino         yellow                           
45   anilino    anilino    hydroxy  4    red                              
46   N-methyl-  N-methyl-  hydroxy  4    red                              
     anilino    anilino                                                   
47   N-methyl-  N-methyl-  benzoyl- 5    reddish                          
     anilino    anilino    amino         yellow                           
48   N-methyl-  N-methyl-  benzoyl- 5    reddish                          
     anilino    anilino    amino         yellow                           
49   N-methyl-  N-methyl-  phenylmer-                                     
                                    4    red                              
     anilino    anilino    capto                                          
50   N-methyl-  N-methyl-  phenylmer-                                     
                                    5    yellow                           
     anilino    anilino    capto                                          
51   butylamino butylamino benzoyl- 4    red                              
                           amino                                          
52   cyclohexyl-                                                          
                cyclohexyl-                                               
                           benzoyl- 4    claret                           
     amino      amino      amino                                          
53   diethyl-   diethyl-   benzoyl- 4    red                              
     amino      amino      amino                                          
54   diisopro-  diisopro-  hydroxy  4    red                              
     pylamino   pylamino                                                  
55   methylmer- methylmer- 4-chlorben-                                    
                                    4    red                              
     capto      capto      zoylamino                                      
56   methylmer- butyl-2-   4-chlorben-                                    
                                    4    red                              
     capto      mercapto   zoylamino                                      
57   methylmer- dimethyl-  phenylmer-                                     
                                    5    yellow                           
     capto      amino      capto                                          
58   methylamino                                                          
                methylamino                                               
                           phenylmer-                                     
                                    5    brown-                           
                           capto         ish                              
                                         yellow                           
59   N-methyl-  N-methyl-  phenylmer-                                     
                                    5    yellow                           
     anilino    anilino    mercapto                                       
60   N-methyl-  N-methyl-  4-chlorphe-                                    
                                    5    yellow                           
     anilino    anilino    nylmercapto                                    
61   N-methyl-  N-methyl-  phenylmer-                                     
                                    8    yellow                           
     anilino    anilino    capto                                          
62   methylmer- anilino    chlorine 3    green-                           
     capto                               ish                              
                                         yellow                           
63   methylmer- 2-chlor-   chlorine 3    green-                           
     capto      anilino                  ish                              
                                         yellow                           
64   methylmer- 3-chlor-   chlorine 3    green-                           
     capto      anilino                  ish                              
                                         yellow                           
65   methylmer- anilino    chlorine 4    yellow                           
     capto                                                                
66   methylmer- o-anisidino                                               
                           chlorine 4    yellow                           
     capto                                                                
67   methylmer- p-anisidino                                               
                           chlorine 4    yellow                           
     capto                                                                
68   methylmer- anilino    chlorine 6    yellow                           
     capto                                                                
69   methylmer- o-toluidino                                               
                           chlorine 5    yellow                           
     capto                                                                
70   p-toluidino                                                          
                p-toluidino                                               
                           chlorine 5    yellow                           
71   methylmer- anilino    chlorine 6(7) yellow                           
     capto                                                                
72   methylmer- p-chlorani-                                               
                           chlorine 6(7) yellow                           
     capto      lino                                                      
73   methylmer- m-toluidino                                               
                           chlorine 6(7) yellow                           
     capto                                                                
74   dimethyl-  dimethyl-  2-chloro-                                      
                                    4    red                              
     amino      amino      benzoyl-                                       
                           amino                                          
75   dimethyl-  dimethyl-  3-chloro-                                      
                                    4    claret                           
     amino      amino      benzoyl-                                       
                           amino                                          
76   dimethyl-  dimethyl-  2-fluoro-                                      
                                    4    claret                           
     amino      amino      benzoyl-                                       
                           amino                                          
77   dimethyl-  dimethyl-  acetyl-  4    claret                           
     amino      amino      amino                                          
78   methylmer- phenylmer- hydroxy  4    red                              
     capto      capto                                                     
79   methylmer- phenylmer- benzoyl- 4    red                              
     capto      capto      amino                                          
80   methylmer- phenylmer- benzoyl- 5    yellow                           
     capto      capto      amino                                          
81   phenylmer- cyclohe-   hydroxy  4    red                              
     capto      xylamino                                                  
82   phenylmer- morpholino hydroxy  4    red                              
     capto                                                                
______________________________________                                    

Claims (10)

What is claimed is:
1. A process for the mass coloration of a thermoplastic in the melt in which the coloration is effected by
incorporating in said thermoplastic in the melt an effective amount of an anthraquinonylaminotriazine of the formula (1) ##STR8## wherein each of X1 and X2 is an alkylmercapto or arylmercapto group or a group of the formula --NR1 R2, in which each of R1 and R2 is alkyl, cycloalkyl, aralkyl or aryl, and R2 can additionally be hydrogen, or R1 and R2 together with the nitrogen atom to which they are attached form a 5- or 6-membered ring or are morpholino, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR9## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1.
2. A process according to claim 1, where in the compound of the formula (1), each of X1 and X2 is a group of the formula --NR1 R2, in which R1 and R2 are alkyl groups of 1 to 20 carbon atoms, alkoxyalkyl groups, cycloalkyl groups of 5 to 6 carbon atoms, benzyl or phenylethyl groups or phenyl groups which are unsubstituted or substituted by chlorine atoms, alkyl or alkoxy groups, each of 1 to 6 carbon atoms, and R2 can additionally be hydrogen.
3. A process according to claim 1, where in the compound of the formula (1), X1 is an alkylmercapto group of 1 to 6 carbon atoms or a group of the formula --NR1 R2, in which R1 and R2 are as defined in claim 2 and X2 is an alkylmercapto group of 1 to 6 carbon atoms.
4. A process according to claim 1, where the compound of the formula (1) is ##STR10##
5. A process according to claim 1, where the compound of the formula (1) is ##STR11##
6. A process according to claim 1, where the compound of the formula (1) is ##STR12##
7. A process according to claim 1, where the compound of the formula (1) is ##STR13##
8. A process according to claim 1, where the compound of the formula (1) is ##STR14##
9. A thermoplastic mass colored by the process according to claim 1.
10. A linear polyester mass colored by the process according to claim 1.
US06/093,644 1978-11-23 1979-11-13 Process for the mass coloration of thermoplastics with anthraquinonylaminotraizines Expired - Lifetime US4292232A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442287A (en) * 1981-07-10 1984-04-10 Basf Aktiengesellschaft Anthraquinone dyes
US4804719A (en) * 1988-02-05 1989-02-14 Eastman Kodak Company Water-dissipatable polyester and polyester-amides containing copolymerized colorants
US5730906A (en) * 1996-07-12 1998-03-24 Exxon Research And Engineering Company Additive combination to reduce deposit forming tendencies and improve antioxidancy of aviation turbine oils (Law406)

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* Cited by examiner, † Cited by third party
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JPS60250052A (en) * 1984-05-28 1985-12-10 Mitsubishi Chem Ind Ltd Colorant for resin

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US3163551A (en) * 1959-05-06 1964-12-29 Ciba Ltd Process for dyeing high-molecular organic products with pigment dyestuffs
US3349089A (en) * 1964-05-06 1967-10-24 Gnii Orch Produktov I Krasitel Triazine dyes of the anthraquinone series
US3459729A (en) * 1963-01-15 1969-08-05 Acna Monoazo triazine containing dyestuffs
US4198205A (en) * 1976-01-21 1980-04-15 Basf Aktiengesellschaft Triazinyl-anthraquinone dye formulations for cellulose or cellulosic fibrous material

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DE1191060B (en) * 1960-06-11 1965-04-15 Cassella Farbwerke Mainkur Ag Process for the production of pigment dyes
DE1644532A1 (en) * 1964-05-05 1969-05-22 Gnii Orch Poluprodktov I Krasi Water-insoluble triazine dyes of the anthraquinone series used for dyeing synthetic fibers
DE2017504A1 (en) * 1970-04-13 1971-10-28 Farbenfabriken Bayer Ag, 5090 Leverkusen Process for the continuous dyeing of synthetic fiber materials
GB1373910A (en) * 1971-12-08 1974-11-13 Yorkshire Chemicals Ltd Anthraquinone disperse dyes

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US3163551A (en) * 1959-05-06 1964-12-29 Ciba Ltd Process for dyeing high-molecular organic products with pigment dyestuffs
US3459729A (en) * 1963-01-15 1969-08-05 Acna Monoazo triazine containing dyestuffs
US3349089A (en) * 1964-05-06 1967-10-24 Gnii Orch Produktov I Krasitel Triazine dyes of the anthraquinone series
US4198205A (en) * 1976-01-21 1980-04-15 Basf Aktiengesellschaft Triazinyl-anthraquinone dye formulations for cellulose or cellulosic fibrous material

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Chemical Abstracts, vol. 77:5828a; 1972. *
Chemical Abstracts, vol. 84:180931v; 1976. *
Chemical Abstracts, vol. 85:193386s; 1976. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442287A (en) * 1981-07-10 1984-04-10 Basf Aktiengesellschaft Anthraquinone dyes
US4804719A (en) * 1988-02-05 1989-02-14 Eastman Kodak Company Water-dissipatable polyester and polyester-amides containing copolymerized colorants
US5730906A (en) * 1996-07-12 1998-03-24 Exxon Research And Engineering Company Additive combination to reduce deposit forming tendencies and improve antioxidancy of aviation turbine oils (Law406)

Also Published As

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DE2966628D1 (en) 1984-03-08
ES8101676A1 (en) 1980-12-16
ES486239A0 (en) 1980-12-16
CA1142670A (en) 1983-03-08
EP0012110A1 (en) 1980-06-11
JPS5573735A (en) 1980-06-03

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